Treated cellulose organic acid ester fibers



United States Patent TREATED CELLULOSE ORGANIC ACID ESTER FIBERS RaymondE. Donaldson and Charles Clayton White,

Kingsport, Tenn, assignor to Eastman Kodak Company, Rochester, N. Y., acorporation of New Jersey No Drawing. Application August 10, 1953,Serial No. 373,455

4 Claims. (Cl. 117-1395) This invention relates to the lubrication andconditioning of textile yarns and filaments, and more particularly tothe lubrication and conditioning of textile yarns and filaments composedof organic derivatives of cellulose such as cellulose acetate, cellulosepropionate, cellulose acetate-propio'nate, and celluloseacetate-butyrate, to render them amenable to a variety of textileoperations such as warping, weaving, knitting, spinning, carding and thelike.

As is well known in the manufacture of yarns, particularly thosecomposed of cellulose organic derivatives, it is necessary to treat theyarn in order to reduce the tendency toward breakage of the individualfilaments or fibers when they are subjected to various mechanicalstrains and to lubricate the yarn in 'order to facilitate handling insuch operations as spinning, twisting, winding, reeling, warping,carding, drafting, combing, weaving, and other operations.

The lubrication of derivatives of cellulose, such as the celluloseesters, is a complex problem, and a diversity of materials has beenemployed to meet the demands or" such lubrication. To those skilled inthe art, it is well known that while certain problems are common to thelubrication of continuous filament yarn and of staple fibers, each hasits own peculiar problems.

After extended investigation, we have found a new chemical compoundwhich may be formulated'wi'th other components to give a fiber treatingcomposition which exhibits improved qualities over comparablecompositions heretofore used in the art.

This invention has as its object to provide *lubricants which areapplicable to treatment of both continuous filament yarns and cut staplefibers as said filaments emerge from the spinningca-binet in whichtheyare formed. A further object is to provide lubricants which aresuitable for continuous filament yarn intended for warping, filling, andknitting. Another object is to provide lubricating and conditioningcompositions which have antistatic characteristics, low kineticfriction, and low slip-stick friction. Another "object of this inventionis to provide lubricants which promote superior bonding between the yarnand warp sizes such as gelatin and 'copolymers of maleic anhydride fandstyrene which are commonly used in the trade.

We have found that certain derivatives of alcohol phosphates whenincorporated into suitable mediums such as mineral oil together with theuse of certain cosolvents provide compositions which may be used toeffectively lubricate filaments and fibers, both continuous filamentsand cut staple. That is, textile material's maybe treated by 'thecompositions to be described in detail herein, to render them moreamenable to subsequent textile operations such as knitting, weaving,winding, card ing, opening, drafting, combing and other operations.

One of the important components of our fibertreating compositioncomprises a .certainreaction product of long chain aliphatic alcoholpartial esters of phosphoric acid. The preferred compound of :this classis illustrated 2,743,193 Patented Apr. 24, 1956 2 by the morpholine saltor salts of laul'yl phosphoric acid partial esters.

We have found that fibers treated with lubricants containing compoundsas just mentioned, and specifically compositions containing salts ofmorpholine and lauryl phosphoric acid partial esters, have unexpectedlyhigh resistance to abrasion when sized with materials such as gelatinand copolymers of maleic 'anhydride and styrene which are commonly usedin the trade. This is one of the novel features of our invention and isbelieved to be new and unobvious.

We preferably use the lauryl partial ester of phosphoric acid, since thelauryl phosphoric acid salt of morpholine gives us the desiredlubricating properties together with a satisfactory viscosity and color.We have found that most of the amine salts of the partial esters of longchain saturated aliphatic alcohols and phosphoric acid are either solidsor waxy or gummy materials. We have found this to be a disadvantage inthe use of these materials for the lubricating and conditioning of bothcontinuous filament and staple fibers made from organic derivatives ofcellulose. However, the morpholine salts of the partial esters of longchain saturated aliphatic alcohols and phosphoric acid are free flowingliquids. This is an unobvious fact and was disclosed to us throughexperimentation. No other amine salts, such as monoethanolamine,diethanolarnine, triethanolamlne, diethylcyciohexylamine,ethylenediamine, or Z-amino-Z-methyll-propauol, of long chain saturatedaliphatic alcohol phosphoric acid partial esters which we have examinedhave exhibited this property of being a free-flowing liquid.

-' For use in preparing compositions described herein we have found thatthe phosphates of long chain aliphatic alcohols, exemplified by laurylphosphate, which compounds may be purchased on the open market, may besatisfactorily used in the'present invention. It is possible, ifdesired, to purchase long chain aliphatic alcohol and phosphoric acid orother source of phosphorus radical and to make the partial estertherefrom. This may be accomplished by reacting the alcohol andphosphoric acid or other phosphor-us derivative together in the presenceof a catalyst, "but such procedure is not required as a number ofpartial ester intermediates may be purchased cornmercially.

The partial ester of phosphoric acid is either prepared or purchased. Itis then reacted with morpholine, as will be described in detailhereinafter, to form the new salt which is used 'hereinin preparing'fiber treating compositions.

We 'h'ave'now found that staple fibers of both cellulose acetate orother organic derivatives of cellulosi'c materials, partially saponified:cellulose acetate or other partially saponified 'oitganicflesters ofcellulose, may be satisfactorily lubricated and conditioned for spinningoperations by the application thereto of =.a single application of alubricating and conditioning composition. This composition preferably iscomprised of a partial ester of phosphoric acid with a long chainaliphatic alcohol, moiphol-ine, and a .long chain aliphatic alcoholtogether with mineral oil in suitable proportions. Our composition isthoroughly dispersed over the fibers in application thereto, and thefibers obtained are completely autistatic so that-a superior degree oflubrication and corn dition'ing is achieved.

Our JIIGVC]. composition preferably comprises from 10-40 parts by weightof the partial ester of phosphoric acid with a long chain saturatedaliphatic alcohol, 2-15 parts by weight of morpholine, 5-l5 parts byweight of fatty alcohols, and 40-70 parts by weight of mineral oilhaving a viscosity from 45-135. (Saybolt Universal seconds at F.)

, In forming said lubricating and conditioning compositions thecomponents are preferably combined by adding the long chain saturatedaliphatic alcohol phosphoric acid partial ester to the mineral oil withstirring, followed by the addition of morpholine, and the addition ofthe fatty alcohol. In some of our compositions, as shown in theexamples, we have found it advantageous to add saturated cyclicalcohols. Also, we have found that other emulsifiers such as terpeneglycol ethers and fatty acid soaps serve as good dispersing agents forthe morpholinium phosphates in mineral oil. After the components aremixed, gentle agitation is continued until a smooth, homogeneous blendis obtained.

In further detail, a partial long chain aliphatic alcohol ester ofphosphoric acid is either prepared or obtained, exemplified by thelauryl partial ester of phosphoric acid. This partial ester has theformula:

The partial ester if desired can be reacted with morpholine as follows:

If desired, the salt may be purified by various procedures as known tothose skilled in the art. The preferred method is to purify the laurylphosphoric acid partial ester and the morpholine before they are causedto react as described above.

The morpholine salt of the partial long chain aliphatic alcohol ester ofphosphoric acid is then formulated into the fiber treating compositionsas already described above.

Example I This cut staple was carded and spun into yarn and was found toprocess well in all operations. One of the important characteristics ofthis lubricant which contributes to the satisfactory processing of cutstaple to which it is applied is the low static electricity developed onthe fibers. This is illustrated in the examples below comparing thestatic electricity on staple'fibers during carding, which have beenlubricated with the composition above, with fibers lubricated withanother type of lubricant, identified as oil A. The units are arbitrary.

Example II The lubricating and conditioning composition described belowwas applied as a 25% aqueous emulsion to denier l9 filament bright yarnand was tested for its static electricity, kinetic friction overporcelain and steel surfaces, and slip-stick friction over a steelsurface. The values were compared with those for a similar yarn treatedwith another lubricant, identified as oil B. The units are arbitrary.

Instant Lubricant B Percent Lubricant on Yarn 2. 38 3.02 StaticElectricity:

Porcelain Surface +1 6 Steel Surface-.- +1 -8 Kinetic Friction:

Porcelain Surface 23 27 24 30 Slip-Stick Friction 17 26 AbrasionResistance of Gelatin Sized Yarn 7O 49 The composition of the lubricantis as follows:

Per cent Mineral oil 58.0 Partial ester of lauryl alcohol and phosphoricacid 25.0 Oleyl alcohol 10.0 Morpholine 7.0

Example III A lubricating and conditioning composition, which isdescribed below, was applied to 75 denier 19 filament bright yarn andwas tested for its static electricity, kinetic friction over porcelainand steel surfaces, and slip-stick friction over a steel surface. Thevalues were compared with those for a similar yarn lubricated withanother lubricant identified as oil C. The units are arbitrary.

Partial ester of lauryl alcohol and phosphoric acid 25.0

Lauryl alcohol 8.0 Cyclohexyl alcohol 6.0 Morpholine 7.0

Although we have indicated in the above examples certain percentages ofoil applied to filaments foruse as cut staple fibers, or continuousfilament yarns, our invention is in no way restricted to these values,nor are the electrical and physical properties given here changedgreatly if the oil content on the filaments is altered over wide ranges.

In the examples stated above, we have indicated that the lubricant wasapplied by means of an applicator roll as the filaments left thespinning cabinet. However, the composition might equally well have beenapplied at other stages of processing and in other operations such astwisting, winding, and reeling, or they might have been applied to cutstaple fibers during any of the processes which are normal to thepreparation of such fibers. Also, although we have indicated that thelubricant may be applied by passing the filaments over a roll, otherdevices which serve to deposit oil on filaments or fibers, such as bywick, spray, or both, may be used.

While in the foregoing disclosure we have specifically referred tolauryl alcohol as this represents the component of ourpreferredcompound, it is possible to use other long chain alcohols inpreparing the partial ester, exemplified by the'following alcohols:oleyl, myristyl,

cetyl, stearyl, etc. Or, it is possible to use mixed alcohols to formthe partial mixed ester.

In place of oleyl alcohol we may use lauryl, cyclohexyl, myristyl,cetyl, stearyl, linolyl, ricinolyl, or mixtures of these. Other changesmay be made in our process and product as exemplified by the following:In place of gelatin or copolymers of maleic anhydride and styrene othersizes may be used such as polyvinyl alcohol or substituted acrylamides.

While the foregoing illustrates certain of the broader aspects of ourinvention for the treatment of, cellulose ester yarn as alreadydescribed above in detail, we prefer to use the morpholine salt of thelauryl partial ester of phosphoric acid inasmuch as certain additionaladvantages and improvements are obtained which are not obtainable byother compounds.

We claim: 7 v

l. Treated cellulose acetate fibers which will exhibit high resistanceto abrasion when sized with a sizing material exemplified by copolymersof maleic anhydride and styrene, said fibers being essentially comprisedof cellulose-acetate, which fibers have applied thereto a treatingcomposition containing a morpholine salt which is a free flowing liquid,said treating composition resulting from the following combination ofmaterials: 25% partial ester of lauryl alcohol and phosphoric acid, 10%oleyl alcohol, 5-7% morpholine, and the major component mineral oil of aviscosity from 45-135 seconds Saybolt Universal at 100 F.

2. Treated cellulose acetate fibers which will exhibit high resistanceto abrasion when sized with a sizing material exemplified by copolymersof maleic anhydride and styrene, saidfibers being essentially comprisedof cellulose acetate which. has applied thereto a treating compositioncontaining a morpholine salt which is a free flowing liquid, saidtreating composition resulting from the following combination ofmaterials: 10-40 parts by weight of lauryl alcohol partial ester ofphosphoric acid, 2 parts by Weightof morpholine, 5-15 parts by weight ofan alcohol from the group consisting of oleyl. lauryl, cyclohexyl,myristyl, cetyl, stearyl, linolyl and ricinolyl alcohols and 40-70 partsby weight of mineral oil of a viscosity of45-135 seconds SayboltUniversal at 100 F.

3. Treated cellulose organic acid ester fibers from the group consistingof cellulose acetate, cellulose propionate, cellulose acetate propionateand cellulose acetate butyrate, which will exhibit high resistance toabrasion 6 when sized with a sizing material exemplified by copolymersof maleic anhydride and styrene, said fibers being essentially comprisedof cellulose organic acid ester which has applied thereto a treatingcomposition containing a morpholine salt which is a free flowing liquid,said treating composition resulting from the following combination ofmaterials: l040 parts by weight of a partial ester of phosphoric acidwith an alcohol from the group consisting of lauryl, oleyl, myristyl,cetyl and stearyl alcohols, 2-15 parts by weight of morpholine, 5-15parts by weight of an'alcohol from the group consisting of oleyl,lauryl, cyclohexyl, myristyl, cetyl, stearyl, linolyl and ricinolylalcohols, and 40-70 parts by weight of mineral oil of a viscosity of45-135 seconds Saybolt Universal at F. i g

4. Treated cellulose organic acid ester fibers from the group consistingof cellulose acetate, cellulose propionate, cellulose acetate propionateand cellulose acetate butyrate, which will exhibit high resistance toabrasion when sized with a sizing material exemplified by copolymers ofmaleic anhydride and styrene, said fibers being essentially comprised ofcellulose organic acid ester which has applied thereto a treatingcomposition containing a morpholine salt which is a free flowing liquid,said treating composition resulting from the following combination ofmaterials: a major amount of mineral oil of a viscosity of 45-135seconds Saybolt Universal at 100 F., 10-40 parts by weight of a partialester of phosphoric acid with an alcohol from the group consisting ofoleyl, lauryl, myristyl,- cetyl, and stearyl, 2-15 parts by weight ofmorpholine, 5-15 parts by weight of an alcohol fromthe group consistingof oleyl, lauryl, cyclohexyl, myristyl, cetyl, stearyl, linolyl andricinolyl alcohols, and wherein the last-mentioned alcohol is differentfrom the alcohol radical in the said partial ester.

References Cited in the file of this patent UNITEDSTATES PATENTS

1. TREATED CELLULOSE ACETATE FIBERS WHICH WILL EXHIBIT HIGH RESISTANCETO ABRASION WHEN SIZED WITH A SIZING MATERIAL EXEMPLIFIED BY COPOLYMERSOF MALEIC ANHYDRIDE AND STYRENE, SAID FIBERS BEING ESSENTIALLY COMPRISEDOF CELLULOSE ACETATE, WHICH FIBERS HAVE APPLIED THERETO A TREATINGCOMPOSITION CONTAINING A MORPHOLINE SALT WHICH IS A FREE FLOWING LIQUID,SAID TREATING COMPOSITION RESULTING FROM THE FOLLOWING COMBINATION OFMATERIALS: 25% PARTIAL ESTER OF LAURYL ALCOHOL AND PHOSPHORIC ACID, 10%OLEYL ALCOHOL, 5-7% MORPHOLINE, AND THE MAJOR COMPONENT MINERAL OIL OF AVISCOSITY FROM 45-135 SECONDS SAYBOLT UNIVERSAL AT 100* F.